Benzoyl acetanilide couplers for color photography



United States PatentO BENZOYL ACETANILIDE COUPLERS FOR COLOR PHUTOGRAPHYFred C. McCrossen, Paul W. Vittum, and Arnold Weissberger, Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N. Y?., a corporationof New Jersey No Drawing. Application June 26, 1952, Serial No. 295,806

7 Claims. (Cl. 95-6) This invention relates to photographic emulsionscontaining coupler compounds for color photography and processes ofcolor photography utilizing coupler compounds for the formation ofphotographic images. In

particular, our invention relates to couplercompounds for forming yellowdye images in color photography.

The formation of colored photographic images by coupling the developmentproduct of aromatic amino developing agents with color-forming orcoupling compounds is well known. In these processes the subtractiveously known couplers in at least one important respect,

that is, the methylene group of the couplers is substituted with achlorine atom with the result that the number of mols of silver haliderequired for the production of one mol of dye from the coupler isreduced from A to 2. The apparent advantage is that such couplersrequire less silver halide to produce a given amount of dye.

It has been found, however, that this advantage is often outweighted bythe serious difliculty that these chlorinated couplers give rise tohigher stain, that is, larger amounts of dye are formed in the unexposedarea of the color developed image. This stain probably arises from oneof two causes: (a) the coupler reacts directly with the unoxidizeddeveloper to form leuco dye which is later oxidized to the dye, or (b)the coupler, which contains an active chlorine atom, oxidizes thedeveloper which then reacts withmore of the coupler in the normal way toproduce dye stain. Whatever the mechanism, the formation of excessivedye stain has been a serious problem Whenever attempts have been made torealize the advantages of the chlorine-containing couplers.

When it is desired to utilize couplers, of the benzoyl acetanilide type,it has been found advisable to employ the o-alkoxy-benzoyl acetanilidecouplers as described in the Weissberger et al. U. S. Patent 2,407,210granted September 3, 1946, in order to obtain yellow dye images of colormost suitable for use with the best cyan and magenta dyes of thesubtractive color processes of color photography, and which couplershave less elfect upon the stability of the yellow dye images than do theunsubstituted benzoyl acetanilides. However, this o-alkoxy substitutionappears to cut down the coupling ability of the coupler and to decreasethe tinctorial power of the dye.

We have discovered that if we employ benzoyl acetanilide couplers inwhich the carbon atom of the active methylene group is substituted by achlorine atom and at 2,728,658 1C6 rimmed Dec. 27, 1955 the same timethe benzoyl group contains an o-alkoxy substituent, stain is reducedapparently by virtue of the presence of the o-alkoxy substituent, andthe coupling ability is increased apparently by the presence of thechlorine substituent on the active methylene group. The two substituentsthus compensate for the deleterious effects of each other. A particularadvantage of our couplers compared to those of the Weissberger et al.patent above resides in the fact that it is considerably easier andaccordingly less costly to produce the ,o-alkoxy andchlorine-substituted compounds than it is to produce the o-alkoxy ando-chloro or dichloro derivatives water.

of the patent. Furthermore, it was not known previous to our inventionthat the u-chlorine substituent would be satisfactory in itself toimprove the coupling ability of the o-alkoxy ben'zoyl acetanilidecouplers.

The coupler compounds of our invention have the following generalformula: 0

I I OR:

'where R represents a mononuclear aryl group substituted EXAMPLE 1 4(u-2-meth0xybenz0yl u chloroacetamido)-3"-(4'- tert. amylphenoxy)benzanilide I Q0 OZHQQNHONHG 0- o on. o

CrHu-t.

o-Methoxybenzoylacet-4-nitroanilide is prepared as follows:

In a 3-l. three-necked flask fitted with a stopper, stirrer, and asteam-jacketed column terminating in a partial condensing still heatcontaining alcohol (Org. Syn. 20, 27) which is connected to awater-cooled condenser set for distillation, are placed 222 g. (1.0mole) of ethyl o-methoxybenzoyl acetate and 800 cc. of dry xylene. 2 g.of anhydrous sodium acetate are added and the mixture is heated to aboil. Heating is discontinued while one-half of 138 g. (1.0 mole) ofp-nitroaniline is added. The flask is stoppered again and the mixturerefluxed for 1 hour, a vapor temperature of 80-90 being maintained.After 30 min, the remaining half of the amine is added and reflux iscontinued for an additional 2.5 hours.

About 200*300 cc. of Xylene should be collected to ensure a completereaction. The xylene solution is then chilled to 5, and the product isfiltered, washed well with 500 cc. of pet. ether, and dried. The yieldis 160-200 g. (51- 64%), M. P. -150. The crude material isrecrystallized from 15 parts of ethyl alcohol in an 80-87% recovery ofyellow-tan crystals which melt at 153-155".o-Methoxybenzoylacet-4-aminoanilide is prepared as follows:

In a 3-l. three-necked flask equipped with a stirrer, stopper, andreflux condenser is placed 62.8 g. (0.2 mole) ofo-methoxybenzoylacet-4-nitroanilide, 300 ml. of ethyl alcohol, 300 ml.of glacial acetic acid, and 300 ml. of The reaction mixture is broughtto a boil while stirring, and boiled for fiveminutes, heating isdiscontinned, and 63 g. of Plast iron powder is added. When the initialreaction subsides, the reaction mixture is refluxed for an additionalten minutes, filtered, and diluted with a solution of 300 ml. of cone.hydrochloric acid and 1 l. of water. The pale yellow solution is chilledto and the precipitate filtered, washed well with 1 l. of cold 3%hydrochloric acid, and dried. 57-582 g. (89-91%) of a pale yellowhydrochloride is obtained. This is mixed intimately with an equal weightof anhydrous sodium acetate and poured with vigorous stirring into 1 l.of ethyl alcohol. (Crystals can be obtained at this point M. P. 103-10565% yield). After stirring minutes, the reaction mixture is diluted with1 l. of water, stirred an additional five minutes, and chilled to 5. Theprecipitate is filtered, washed with 1 l. of cold 50% alcohol, anddried. The yield is 47 g. (83%) of tan crystals which melt at 90-92. A90% recovery of material melting at 100-102 can be obtained bydissolving the material in 10 parts of ethyl alcohol and diluting with 5parts of water.

In an alternate procedure o-methoxybenzoylacet-4- nitroanilide isreduced with hydrogen overRaney nickel. Crystallization from alcoholyields product sintering at 98 and melting 102-106 C. Recrystallizationgives the amino compound melting 102l04 C.

4 (2 methoxybenzoylacetamido)-3"-(4-tert. amylphenoxy) benzanilide isprepared as follows:

In a 500 ml. three-necked flask equipped with a stirrer and stoppers, isplaced 28.4 g. (0.1 mole) of o-methoxybenzoylacet-4-aminoanilide and 250ml. of 5% sodium acetate-acetic acid solution. To the well-stirredsuspension 30.3 g. (0.1 mole) of m-(p-tert. amylphenoxy) benzoylchloride is added all at once. The suspension clears and the productbegins to separate almost immediately. The mixture is stirred untilstirring becomes impossible (ca. 1 hour) and then allowed to sit for anadditional hour. The precipitate is filtered, washed with 500 ml. of 50%acetic acid, followed by 500 ml. of water, and dried. The yield is50.5-52 g. (92-95%) of light yellow powder which melts at 143-145".Recrystallization from methanol and dioxane is assumed to yieldpolymorphs M. P. 147-149 C. and 163-165 C. respectively.

The desired product I was prepared as follows:

In a 1-1. three-necked flask equipped with a stirrer and droppingfunnel, is placed 27.5 g. (0.05 mole) of 4-(2-methoxybenzoylacetamido)-3-(4 tert. amylphenoxy) benzanilideand 500 ml.of dry chloroform. 4.05 ml. (0.05 mole) of sulfuryl chloride is addedrapidly with stirring and the reaction mixture is stirred until it setsto a thick paste. The reaction mixture is then heated until solution iscomplete, filtered, and allowed to cool slowly until crystallization isalmost complete. It is then cooled to 5, filtered, washed with petroleumether, and dried. The yield is 21.3-24.5 g. (73-80%) of a White powderwhich melts 163-165 EXAMPLE II 4-(a-Z'-methoxybenzoyl-a-chloroacetamido-2 ,4"-diterL-amylph enoxyacetanilide II Qooenoomr 0H3 C1 (nun-z.

4 (2 methoxybenzoylacetarnido)-2",4"-di-tert. amylphenoxyacetanilide isprepared as follows:

In a 1-liter flask equipped with a stirrer is placed 250 ml. of a 5%solution of anhydrous sodium acetate in glacial acetic acid and 28.4 g.(0.1 mole) of 4-(2-methoxybenzoylacetamido)-aniline. The slurry isstirred for ten minutes, and then 31.1 grams (0.1 mole) of (the acidchloride) 2,4-di-t. amylphenoxyacetyl chloride is added all at once. Thereaction becomes clear and, after stirring ten minutes, sets to a heavyslurry. When stirring becomes impossible (after about five to tenminutes), the sludge is filtered, washed well with water, and dried. Theyield of crude light yellow (or white if colorless acid chloride isused) product, M. P. 178-180", is 51 g., which is 91% of the theoretical55.8 g. This is recrystallized from 70 parts of methyl alcohol to yield33 g. (59%) of material which melts 188-190.

In an alternate procedure 2,4-di-t. amylphenoxy acetyl chloride isreacted with p-phenylene diamine and the product treated as follows:

A solution of 17 g. (0.0445 mole) of the product4-amino-u-(2,4'-di-tert.-amylphenoxy)acetanilide in 200 cc. ofhistological xylene in a 500 cc. flask fitted with a steam-jacketedstill head was heated to boiling. Then 9.9 g. (0.0445 mole) of ethylo-methoxybenzoylacetatewas added in one portion. Refluxing was continuedfor one hour while 2.5 cc. of ethanol was collected. The xylene solutionwas filtered and chilled. The product was collected and washed with cc.of petroleum ether. The yield of white crystals, M. P. 190-192", was 18g. (74%).

The desired product II is prepared as follows:

In a 1-liter flask equipped with stirrer is placed 37.5 g. (0.0672 mole)of 4- (2'- methoxybenzoylacetamido)-2",4"-di-tert.-amylphenoxyacetanilide and 250 ml. of dry chloroform. Themixture is stirred ten minutes and then 5.45 ml. (0.0672 mole) ofsulfuryl chloride is added all at once. The temperature rises from23-30" and complete solution is obtained immediately. The reactionmixture is stirred two hours, then 500 ml. of dry ether is added withstirring and chilling. At 0-5 the product is filtered, washed withether, and dried. 35 g. (89%) of yellow product is obtained which meltsat -147. Upon crystallization from 30 parts of methyl alcohol, 28 g.(70%) of oft-white powder is obtained which melts at 153155.Recrystallization again from 15 parts of 3A alcohol produces 22 g.(55%), M. P. 154-15 6.

EXAMPLE III ot-o-Methoxybenzoyl-a-chloro-4- a (2,4-di-tert.-amylphn0xy)-n-butyramido1 acetanilide III Cl OCH; l

CxsHu t.

lr,H1 i..

a+(2,4di-tert. Amy1phenoxy)-n-butyryl chloride is prepared as follows:

In a 1-liter three-necked flask equipped with a stirrer, thermometer,and reflux condenser are placed 234 g. (1.0 mole) of diamylphenol, 40 g.(1.0 mole) of sodium hydroxide (pellets) in 100 ml. of water and 83 g.(0.5 mole) of a-brornobutyric acid. After stirring at reflux for 1.5hours, the reaction mixture is diluted with 350 ml. of benzene and 500ml. of water. The mixture is acidified with 110 ml. of concentratedhydrochloric acid and the benzene layer is washed with 2 x 500 ml. ofwater. The benzene is removed in vacuo and the syrupy residue isdistilled. About 155 g. of diamylphenol (B. P. 106/ 1 mm.) and 25 g. ofproduct (B. P. 152-158/1 mm.) are obtained.

The acid (25 g.) is refluxed one hour in five parts of thionyl chloride.The excess thionyl chloride is removed in vacuo and when the viscousresidue reaches constant weight the acid chloride is ready for use. Theyield is ca. 25% based on diamylphenol not recovered.

a-o-Methoxybenzoyl-4-l a (2,4-di-tert.-amylphenoxy)n-butyramidolacetanilide is prepared as follows:

In a 50 ml. three-necked flask equipped with a stirrer is placed 2.84 g.(0.01 mole) of o-methoxybenzoylacet-4- aminoanilide prepared above and1.0 g. (0.01+ mole) of sodiumacetate in 25 ml. of glacial acetic acid.With rapidstirring, 3.4 g. (0.01 mole) ofa-(2,4-di-tert.-amylphe'noxy)-n-butyryl chloride is added all at once.The

' longer.

7 reaction mixture becomes murky immediately and is stirred for threehours at room temperature. With goodstirring the reaction mixture isdrowned in 300 ml. of

The desired product III is prepared as follows:

In a '500 ml. round bottom flask equipped with a stirrer is placed 35.5g. (0.0605 mole) of a o-methoxy benzoyl-4-[a 2,4 di-tert.-amylphenoxy)-n-butyramido acetanilide in 200 ml. of dry chloroform, and 4.9 m1.(0.0605 mole) of sulfuryl chloride is added dropwise with stirring. Thereaction mixture is stirred overnight. The chloroform is'rernovedinvacuo and the oily residue is dissolved in 300 mlpof methanol. Aftercooling to -5, a white solid separates which is filtered, washed with 50ml. of cold methanol, and dried. The crude product (26.1 g., 70%, M. P.80-90") is recrystallized from parts of methanol to give 22 g. (59%) ofmaterial which melts at 88-90.

This coupler compound is outstanding among the other couplerscontemplated by our invention because the three terminal alkyl groupsapparently enhance its solubility in coupler solvents used fordispersing the coupler in gelatino-silver halide emulsions.

EXAMPLE IV The precipiof snow white solid which EXAMPLE Voi-(o-Methoxybehzoyl) cL-chlor -S-[u -(2,4 ditent-amylphenoxy)-n-butyramid0]acetanilide V eon. llrnoooncnzom isprepared by a procedure similar to Example III with the substitution ofo-methoxy-benzoylacet-3-aminoanilide foro-methoxy-benzoylacet-4-aminoanilide as follows:

u- (2,4-Di-tert.-amylphen0xy -3-nitrobutyranilide Dimethyl 5-{4(2,4-di-tert.-amylphenoxy) -3-{u-[4-(0t-0-. anisoyl-a-chloroacetamido)phenaxy] acetamidojibenzmcoooU-oooon.

amid0}is0phthalate IV Q4: OEHC ONHO-O omooNH- UsHu-t.

a (o Methoxybenzoyl)-4-{ [2 (2,4-di-tent.'-amylphenoxy) -5 3 5-dicarbomethoxyp henylcarbamyl )phenylcarbamyl]methoxy}-acetanilide isprepared by first reacting 4-(2,4-di-tert.-amylphenoxy) 3 nitrobenzoylchloride with 3,5-dicarbomethoxy aniline; reducing the nitro group ofthe product followed by reaction of the resultant amino group with4-nitrophenoxyacetyl chloride. The nitro group of this product is thenreduced and the product condensed at the resultant amino group withethyl-omethoxybenzoyl acetate.

The desired product IV is obtained as follows:

Ten grams (0.0113 mole) of a-(o-methoxybenzoyD-[2-(2,4-di-tert.-amylphenoxy) 5 (3,5 dicarbomethoxyphenylcarbamyl)phenylcarbamyllmethoxy acetanilide is dissolved in 150ml. of dry chloroform and cooled to 5 C. At this temperature there isadded in 10 minutes 1.75 g. (0.0113 mole) of sulfuryl chloride dissolvedin ml. of dry chloroform. The solution is stirred during the addition ofthe sulfuryl chloride and for one hour The reaction mixture is thenheated to 50 C. for 5 minutes and the solvents removed under diminishedpressure. The residue is crystallized from ethyl acetate, thus obtaininga good yield of white product, melting at 223-224 C.

An addditional recrystallization from cc. of alcohol gave 18 g. of Whitecrystals, M. P. 84-86".

. Anal. -Calcd. for C2sH3sN204! N, 6.35; found: N, 6.4.

3-am inc-a (2,4 -di tert-amylph enoxy) butyrtm ilide ao-Methoxybenzoyl-3- ot-(2,4-di-tert-amylph enoxy butyramido acetanilide To a refluxingsolution of 11.5 g. of 3-amino-a-(2,4 di-tert-amylphenoxy)butyranilidein 100 cc. of histological xylene was added 6.2 g. of ethylo-methoxybenzoylacetate. The solution was refluxed for two hours in sucha way that the ethanol distilled under reduced pressure.

The gummy residue was stirred under petroleum ether to give 13.5 g. ofan amorphous solid melting above 60".

It was not obtained in a crystalline form.

The desired product V is obtained as follows;

To a solution of g. of e-(o-methoxybenzoyl)-3-[a-(2,4-di-tert-amylphenoxy)butyramido]acetanilide in cc. of chloroform wasadded 0.7 cc. of sulfuryl chloride dropwise with shaking. The solutionwas allowed to evaporate slowly at room temperature. The yellow gum wassoluble in alcohol, benzene, acetonitrile, chloroform, and carbontetrachloride. It was insoluble in water and petroleum ether. Thematerial did not crystallize.

Compounds having the general formula given above in which R is anortho-substituted phenyl group are not readily prepared by the methodsof the preceding examples.

Coupler iV has the unusual property that the spectral absorption oftheazomethine dyes made therefrom by color development, are particularlysharp, that is, the absorption in the blue region of the spectrum isconfined to a relatively narrow range of wavelengths which is an effectlong sought in dyes for color photography. The etiect is due, at leastin part, to the alkoxy group in the p-position of acetanilide nucleus ofthe coupler.

This coupler is of particular value in those cases where it is desirableto incorporate a coupler into an emulsion by use of alkali rather than acoupler solvent. Accordingly, the ester groups of the above coupler arefirst hydrolyzed in alcoholic alkali in a well known manner, then thecoupler is incorporated into an emulsion as the alkali metal salt.

All of the couplers of the invention may be incorporated into emulsionlayers by the method of Fischer U. S.

Patent 1,055,155, or by means of coupler solvents by the methods ofMannes et al. U. S. Patent 2,304,940, granted December 15, 1942, and.lelley and Vittum U. S. Patent 2,322,027, granted June 15, 1943.

As is apparent, the couplers of the invention are primarily useful inmultilayer color films and for that purpose the couplers areparticularly efficacious since they show relatively little diffusion ingelatin emulsion layers especially when the substituent in thep-position of the acetanilide nucleus is sizeable.

In the development of exposed photographic silver halide emulsion layersusing the couplers of our invention, any color-forming developercontaining a primary amino group may be used. These include developershaving two primary amino groups as well as those having one of the aminogroups substituted or having substituents in the ring, such as the alkylphenylene diamines. compounds are usually used in the salt form, such asthe hydrochloride or the sulfate which are more stable than the aminesthemselves. The suitable compounds are diethyl-p-phenylenediaminehydrochloride, monomethyl-pphenylenediamine hydrochloride,dimethyl-p-phenylenediamine hydrochloride, andZ-amino-5-diethylaminotoluene hydrochloride. The p-amino phenols andtheir substitutionproducts may also be used where the amino group isunsubstituted. All of these developers have an unsubstituted amino groupwhich enables the oxidation products of the developer to couple with thecolor-forming compounds to form a dye image.

Our development process may be employed for the pro- These mixture ofsilver halide and the coupler compound diduction of colored photographicimages in layers of gelatin or other water-permeable colloidal carriers,such as albumin, collodion organic esters of cellulose, or syntheticresins. The carrier may be supported by a transparent medium such asglass, a cellulose ester or synthetic resin or a non-transparentreflecting medium such as paper or an opaque cellulose ester. Theemulsion may be coated as a single layer on the supoprt or as one of anumber of superposed layers on one or both sidesof'the support. Thesuperposed layers may bedifferentially sensitized as is conventional incolor photography.

What We claim is: p

.1. A photographic silver halide emulsion comprising a mixture of silverhalide and a coupler compound of the class consisting of 4-ct-Z-methoxybenzoyl-a-chloroacetamido) -3"-(4-tert.

amylphenoxy) benzanilide 4 (a 2-methoxybenzoyl-a-chloroacetamido)-2",4"-ditert. amylphenoxyacetanilide a 0 Methoxybenzoyla-chloro-4-[a-(lA-di-terh-amylphenoxy -n-butyramido acetanilide Dimethyl5 {4-(2,4-di-tert.-amylphenoxy) -3-{a- [4-( 01-0- anisoyl -u.-chloroacetamido) phenoxy] acetamido}-benzamido}isophthalate a (oMethoxybenzoyl)a-chloro-3-[a-(ZA-di-tert. amylphenoxy) -n-butyramido]acetanilide .mixtureof silver halide and the coupler compound 4-(oc- 2methoxybenzoyl oz chloroacetamido)-2",4-di-tert.-amylphenoxyacetanilide.

4. A photographic silver halide emulsion comprising a mixture of silverhalide and the coupler compound Ot-O- methoxybenzoyl on chloro 4[a-(2,4-di-tert.-amylphenoxy -n-butyramido] -acetanilide.

5. A photographic silver halide emulsion comprising a methyl 5-{4-2,4-di-tert.-amylphenoxy) -3-{cc- [4 a-o-anisoyl a chloroacetamido)phenoxy]acetarnido}benzamido}isophthalate.

6. A photographic silver halide emulsion comprising a mixture of silverhalide and the coupler compound a-(omethoxybenzoyD-a chloro3-[a-(2,4-di-tert.-amylphenoxy -n-butyramido] -acetanilide.

7.. A method of producing a colored photographic image in a silverhalide emulsion layer, which comprises exposing said layer anddeveloping it with a primary aromatic amino silver halide developingagent in the presence of a coupler compound designated in claim 1.

References Cited in the file of this patent

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION COMPRISING A MIXTURE OF SILVERHALIDE AND A COUPLER COMPOUND OF THE CLASS CONSISTING OF4-(A-2''-METHOXYBENZOYL-A-CHLOROACETAMIDO)-3"-(4''''''-TERT.AMYLPHENOXY) BENZANILIDE 4-(A-2''-METHOXYBENZOYL-A-CHLOROACETAMIDO)-2",4"-DITERT. AMYLPHENOXYACETANILIDE A - O - METHOXYBENZOYL -A-CHLORO-4-(A-(2,4-DI-TERT-AMYLPHENOXY)-N-BUTYRAMIDO)ACETANILIDEDIMETHYL 5-(4-(2 4-DI-TERT-AMYLPHENOXY)-3-(A-(4-(A-OANISOYL-A-CHLOROACETAMIDO)PHENOXY)ACETAMIDO)-BENZAMIDO)ISOPHTHALATE A - -(O -METHOXYBENZOYL)A-CHLORO-3-(A-(2,4-DI-TERT.AMYLPHENOXY)-N-BUTYRAMIDO)ACETANILIDE.